Anthraquinone lactam dyestuffs



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aerator anrnnaanmonn rnornvr nrns'rnrrs Samuel lEllingworth, Norman lfilulton Haddoch,

lFranlr Lodge, and Uolin llenry ltumsden, Blackley, Manchester, England, assignors to "imperial Chemical industries lidmited, a corporation oil Gil-eat lhritain ltl'o lllirawing. application liliecember M, i933, Serial No. 'IHWAllti. In Great Britain December '2' (Claims.

in copending U. S. application Ser. No.689,lll4l,

filed September Ill, 1933, which has eventuatedin which AQ stands for anthra uinone or substltuted anthraquinone.

We have now found that other dyestuds having the l'ollowing formula:

in which AQ stands as before "lor anthra uinone or substituted anthraquinone, R and R stand lor hydrogen, alkyl, aryl or arallryl groups, but lit and R" not both standing for hydrogen at the same time, may be produced in a manner similar to that described in the above referred to application. The groups attached to the -Cel-l'3= group are located as indicated in the formula, i. e., the -NH2 and S-- are ortho to one another and the AQ-NI-l-CO- is located at any other position in the ring.

We have found that the principles involved are capable of broader application and according to the present invention we make and reduce a dinitro-diaryl-disulphide-dicarboxy -amino anthraquinone as described in U. S. Patent 1,975,-

lliil, and we treat the product with a halogeno acid ol the general formula:

nai-o-poln RI RI! lEt and R" having the significance given above,

but R and R" not both standing for hydrogen at the same time; or we cause to interact an amino-anthraquinone or substituted amino-an thraquinone with a lactam of the general formula:

COzHarylN IGO CRR R and R" having the significance given above but R and R'g not both standing for hydrogen,

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(or. e -m of a nitro-carbory-phenyl thio ester oi the general formula:

COrH-CeHa-Na where R and B" have the significancegiven above and Y stands for alkyl, aralkyl or the like, and we hydrolyze the ester group and subsequently or simultaneously reduce the nitro group.

The anthraquinone dyestuffs obtained in accordance with the invention are particularly valuable tor-the production of shades fast to light,

washing, potting and milling on animal fibers, the dyestuffs being applied in a weak acid bath and subsequently lactamized on the fiber as described in U. S. Patent 1,975,061. The dyestufls are also valuable for the manufacture oi pigments and for use as vat dyestufis.

The invention is illustrated, but not limited, by the following examples, in which the parts are by weight.

Example 1 3.1 parts of ethyl-2-nitro-d-carboxy-phenylthioglycollate, l6 parts of thionyl chloride and parts of nitrobenzene are warmed with stirring at 110 forZ hours. To the clear solution of the acid chloride are added 2.2 parts of lamano-anthraquinone and the mixture is stirred lll at 130-135" for 1 hour. Hydrogen chloride is evolved. The resulting clear solution is cooled to 3d", whereupon the acyl-amino-anthraquinone separates; it is filtered oil and washed with nitrobenzene and alcohol. This intermediate compound is an orange yellow crystalline substance. For hydrolysis 2 parts of this compound are dissolved in 60 parts of boiling glacial acetic acid, and 7 parts of hydrochloric acid of strength are gradually added, with good stirring. Boiling is continued for 30 minutes. The mixture is then cooled and the carboxylic acid filtered off and washed with water. The acid is now reduced by mixing it with parts of alcohol and 6 parts of sodium sulphide crystals and boiling for five minutes. The mixture is cooled a little hydrogen peroxide is added if necessary, and the new dyestufi filtered and washed with 'weak" brine; it'is dissolved in hot water, filtered from any insoluble matter that may be present, and precipitated by addition of salt. The dyestuff is identical with that described in Example 1 of U. S. Patent 1,975,061.

Example 2 4.8 parts of the intermediate compounds obtained from 2,2-dinitro-4,4'-dicarboxy-diphenyl- Kill I wat and the mixture is heated to 65-7ll} and sti ed at that temperature for one hou". 20 parts of salt are added to the solution. .It

is cooled, and the amino mercaptan is filtered off and pressed. This intermediate is dissolved in 92 parts of hot water and mixed with an aqueous solution made from 4.8 parts of i-b-rornopropionic acid and the appropriate amount of sodium hydroxide or carbonate. The mixture is heated at 90 until. interaction is complete, alkali being added as needed to keep it alkaline. Salt is added. lhe solution is cooled and the product is filtered off, washed. with brine, and dried. The new dyestuff is a yellowish brown substance. dyes wool from an acetic acid bath in oran e yellow shades, changing on after-treatment with weal: mineral acid to a bright golden yellow exceedingly fast to washing, milling and potting.

It is of course understood that this invention is not limited to the use of only the dinitrodiaryl-disulphide-dicarhoizylic acid above mentioned, but contemplates the use of any of the compounds mentioned in U. 53. Patent 1,975,661.

I" is also understood that compounds of the above formula may he produced by the methods described in U. 5. Patent 1,975,061 by substituting for the chloroacetic acid therein used acids having the formula:

HalO-COOH in which R and R represent hydrogen, alhyl, aryl or aralhyl groups, but '3. and Ft not both. standing for hydrogen at the same time.

Example 3 l22 parts of the intermediate compound ohtained om 2:2-dinitro-e:4-dicarboxydiphenyl disulphide and l-ainino--metho -anthraquinone as described in Example 2 oi U. S. Patent 1,975,061 are made to a smooth paste with zoo parts or water. 50 parts of sodium sulphide crystals are added and the mixture stirred at 65-70" C. for half an hour. On cooling the sodium inercaptide is precipitated and this is filtered off and washed with salt solution. This intermediate is dissolved in ace parts of water and to the solution are added 14 parts of B-bromo-n butyric acid which have previously been dissolved in water and neutralized with the appropriate amount of sodium carbonate. A further lil parts of sodium carbonate are added and the mixture warmed at 90-95 for three quarters of an hour. After cooling to 70, the dyestuff is filtered off and washed with dilute salt solution. The new dyestufi dyes wool from an acetic acid bath in orange shades changing on after-treatment with weak mineral acid to a bright scarlet shade of excellent fastness to washing, milling, potting and light.

Example 4 By substituting the appropriate quantity of a-brorno-n-butyric acid for the a-bromopropionic acid in Example 2, a dyestuff is obtained which dyes wool from an acetic acid bath in orange shades which changes to an orange-yellow on treatment with hot dilute mineral acid. The dyestuff has excellent fastness to washing, milling and potting.

Example 5 pats of the intermediate compound obtained from 2 Z'-dinitro-4 :a-dicarboxydiphenyldisul phide and l-anoino-4-methylamino-anthraquinone by the method described in U. S. Patent 1,975,061 and heated with 12 parts of sodium sulphide crystals in parts of methylated spirits at the boil for 26 minutes. The mixture is poured into 100 parts of water containing 6 1; .rts oi a-bromo-n-butyric acid neutralized with the ap propriate quantity of sodium carbonate. A further 5 parts of sodium carbonate are added and the temperature raised to 90 for a quarter of an hour. 15 parts of common salt are added and after cooling to 50 the dyostuif is filtered. The dyestuff can be purified by redissolving in boiling water, filtering to remove insoluble matter and reprecipitating by the addition of salt.

When dyed from an acetic acid bath the dye stuff has good affinity for W001 and the shade after treatment with hot dilute mineral acid is reddish-blue. It has excellent fcst ness to light, potting, milling and washing.

What we claim is:

1. Compounds of the following general formula wherein AGE stands for an anthraquinone radical, i=3, and R" stand for hydrogen, or an allryl, aryl or arallryl group, but it R" not both standing for hydrogen at the same time, and wherein a: and 3! represent a bond linking the ll and C atoms or :0 represents hydrogen and 2; represents OH.

2. Compounds which in the form of their free acids have the following general formula NHiu AO -NHCOaryl s-o-o 0213(2) R! RI! in which AQ stands for anthraquinone or substl tuted anthraquinone, R and R" stand for hydrogen, or an alkyl, aryl or aralkyl group, but P. and R" not both standing for hydrogen at the same time.

3. Compounds of the following general formula:

in which AQ stands for anthraquinone or substitutecl anthraqulnone, R and R" stand for hydrogen, or an alkyl, aryl or arallryl group, but R and R" not both standing for hydrogen at the same time.

i. In the preparation of dyestuffs oi the class described, the steps which comprise reacting a dlnltro -diaryl disulphide dicarboxy amino anthraquinone with a halogeno acid or the general formula:

mn-o-o 0 0H Q R! RI! in which R. and R" stand for hydrogen, or alkyl,

aryi or araihyi groups, but R and h." hot hath standing for hydrogen at the same time.

ii. In the preparation or dyestwds having the toiiorvine' general formula:

' New AQ-NH-CO-Cdila I s-o-omma RI ml! in which ha stands tor anthradiiihone or substituted anthraeninone, R and R stand for hydrogen, aiiryl, aryi or araihyi groups, hurt R and 1%" not tooth standing for hydrogen at the same time, the process which comprises reacting an no-anthraqninone eomponnd with a halide ot" a nitro-earhony-nhenyi-thio ester ot the here- I erai formula:

where R and id" have the sienitieanee given ahoye, and Y stands tor an aihyi or araihyi group,

hydroiyzine the ester group and redaeine the nitro group to the corresponding amine.

d. The process for dyeing hher which eoni= prises anplyingthereto a solution of a compound of the general formula:

AQ-NHU 0-aryl s-o-oooa a L X to laetamize the dyestnfi, thereby hiring it to the iiher.

7. Fiber dyed with a compound as defined in eieim i.

SAMUEL EWNGWORIH. NURMAN HULTON HADDUCK. FR LUDGE.

(COLIN f-MNRY 

